Reflux ratio control



Jfine 12, 1951 s. GAL-STAUN ETAL 5 REFLUX RATIO CONTROL Filed Sept. s, 1948 2 Sheets-Sheet 1 INVENTORS LIONEL S. GALSTAUN EDWARD R. KEEVER AGENT June 12,,l951 L, s. ALs-r N 2,556,752

REFLUX RATIO CONTROL Filed Sept. :5, 1948 2 Sheets-Sheet 2 INVENTORS LIONEL S. GALSTAUN EDWARD R. KEEV ER AGENT Patented June 12, 1951 REFLUX RATIO CONTROL Lionel S. Galstaun, San Francisco, and Edward R. Keever, Martinez, Califi, assignors to Tide Water Associated Oil Company,

San Francis'co, Calif., a corporation of Delaware Application September 3, 1948, Serial No. 47,728

3 Claims.

This invention relates to distillation columns, and more particularly to means for automatically attaining desired reflux ratios during distillation and automatically changing the reflux ratio during critical periods of operation. The invention is primarily adapted for use in conjunction with batch stills of the type commonly employed in laboratory investigations, although it also has utility in certain commercial distillation operations especially where close fractionation of product is desired. a

It is an object of the invention to provide means for automatically maintaining a higher reflux ratio in a distillation column during those periods when distillate product is changing and a lower ratio during those periods when the composition of the product is constant.

Another object is to provide automatic means to cutoff, or diminish, the product draw-off from a distillation column during periods of temperature rise.

An object of a specific embodiment of the invention is to provide means for coupling a thermocouple operated temperature recorder to the reflux ratio control apparatus of a distillation column to change the reflux ratio upon a change of temperature.

Other objects will be apparent from the following description.

In the laboratory investigation of mixtures of distillable liquids, and in certain commercialoperations where such liquids are to be separated into components, it is common practice to distill these in a batch type still provided with an adequate distilling column containing packing, bubble plates, or other contact means. The vapors from the top of the contact material are usually condensed and a portion thereof returned to the column to provide reflux while a second portion is withdrawn as distillate or product. The ratio of the quantity of condensate returned to the column to the quantity of product withdrawn is termed the reflux ratio;

In order to diminish the amount of labor, and to attain more uniform distillation, various equipment has been developed to control automatically the rate of distillation and to maintain a constant reflux ratio. Likewise, various automatic equipment is known for separating the distillate into cuts so that several products from the still can be segregated.

Depending upon the closeness of fractionation desired, the reflux ratio required may vary from 1:1 to as high as 20:1, or even higher. Even with highly eflicient fractionating columns, high reflux ratios are required when it is desired to obtain a close fractionation of product such as is required for laboratory investigations or in the commercial separation of organic liquids of high purity. An especially high reflux ratio is needed during the period of transition of one product to another, whereas a substantially lower reflux ratio may be used during those periods when the composition of the product is constant With an automatic still of the usual type, unless an attendant is present to adjust the reflux ratio as required, the reflux controls must remain set at the high ratio needed during product changes and the entire distillation must be conducted at this ratio. Consequently, the time normally required to complete a distillation in an entirely automatic still is far greater than when the reflux ratio can be reduced during periods of constant product composition.

In accordance with the present invention the reflux ratio of an automatic still may be set at the low value desired for constant product composition. and when the slightest change in composition occurs, the reflux ratio will be automatically doubled, tripled, or increased to any desired extent. After the composition of the product becomes constant again, the normal reflux ratio is automatically reestablished. It is thus seen that, by use of the invention, a large amount of time may be saved in the distillation of a batch of material in an automatic still.

The invention will better be understood by reference to the drawings, Figure 1 of which illustrates in diagrammatic form mechanical and electro-inechanical apparatus embodying principles of the invention.

Figure 2 is a schematic diagram illustrating a preferred form of electronic apparatus exemplifying features of the invention.

Referring to Figure 1, there is represented b the numeral l a sectional view of the head of a laboratory type distillation column, which is equipped with finger type condensing coil 2 positioned to condense vapors which rise in head I and to direct the condensate into valve 3 and draw-ofi line l. For controlling the reflux ratio, valve 3 is intermittently opened and closed by needle 5 which is operated by solenoid B. When the circuit between terminals 1 and 8 is closed (as will be explained later) solenoid 6 is energized by current controlled by any suitablev timing device, which is illustrated by cam 9, operated by clock-work it and actuating contact points ll. When the lobe of cam 9 depresses its follower, contact points H are closed permitii ting current to pass through solenoid B which, upon becoming thus energized, raises valve pin opening valve 3 and causing liquid condensing on surface of coil 2 to be discharged through drawoff line 4. When the lobe of cam 9 passes beyond its follower, contacts H open breaking the circuit to solenoid B and permitting pin 5 to close valve 3. When valve 3 is closed, the condensate is unable to enter line i and consequently drains down column head i and returns to the fractionating column (not shown) as reflux. It is apparent, therefore, that the reflux ratio or" the column may be set at any desired value depending upon the ratio of the length of periods dur ing which contact points It are open and closed.

Various timing devices are available on the market and the form depicted by cam 9, contact H and clock-work i9 is for the purpose of simplicity of illustration and, per se, forms no part of the present invention. Likewise, stillhead I, condensing coil 2, and valve 3 are illustrative of a commonly used form of reflux control, but the particular design thereof shown in Figure l is merely for illustrative purposes to explain the operation of the invention.

In accordance with the invention, during periods when the product obtained from line i is changing in composition, the scheduled openings of valve 3 are interrupted thereby causing a greater proportion of condensate to be returned to the column as reflux, thus increasing the reflux ratio at a time when high rates of reflux are desirable.

To this end there is sealed (or otherwis introduced) into column-head l a thermocouple i2 located at any point where control may be desired. The cold junction 13 of the thermocouple is positioned in a constant temperature bath (not shown) or a suitable cold junction compensating device is included in the thermocouple circuit Terminals Hi and E5 of the thermocouple are connected to a potential-balancing device, illustrated by slide-wire potentiometer it, the slide ll of which is operated by worm l8 and motor l9. In series with the thermocouple circuit there is placed a potential responsive means illustrated by galvanometer 20, the needle of which operates contacts 2i and 22 depending, respectively, upon whether the temperature of thermocouple i2 is above or below that corresponding to the position of slide ll. Motor l8 is equipped with two windings so arranged that passage of current through one winding causes the motor to rotate in one direction and passage of current through the other winding causes the motor to rotate in the opposite direction.

Accordingly, should the temperature of ther mocouple [2 rise above that corresponding to the electrical potential between slide El and terminal 23 of potentiometer i6, current will flow through galvanometer 26 causing contact 2i to close and permit current from battery 24 to flow through leads 25 and 2? of motor [9 which will then rotate worm l8 raising slide ll until a balance is reestablished. Likewise, should the temperature of thermocouple 12 fall below that corresponding to the potential between slide ii and terminal 23, the current through galvanometer will cause contact 22 to close, permitting current from battery 24 to flow through terminals 25 and 25 of motor 19. Motor l9 will then rotate worm 18 in the reverse direction lowering slide i? until balance is established.

If desired, suitable relays of either the electromechanical or thermionic type may be introduced in the circuits of motor 19 for the puri pose of reducing the currents handled by contacts 2i and 22, or to control the direction of rotation in the event an ordinary reversible motor is substituted for motor IS.

A feature important to the operation of the invention is relay 28 which is included in the circuit controlled by contact 2|. It may be placed in series (as shown) or in parallel with motor terminals 25 and 21 as the characteristics of the current supplied by battery 24 may dictate. If desired, the current supplied to relay 28 may be amplified by suitable relays. Suffice it to say, for the present, that the circuit is such that relay 28 will operate upon a flow of current through galvanometer 29 corresponding to a rise in temperature of thermocouple I2.

It will be readily apparent to anyone familiar with the art of recording potentiometers that the balancing device depicted in Figure 1 by potentiometer I6, galvanometer 29, motor I9 and the described circuits is similar to well known types of recording and/or indicating potentiometers. In fact, for. the purposes of the invention any type of balancing potentiometer may be substituted for galvanometer 20, potentiometer l6, and motor [9, providing that provision is made to supply current to relay 28 during any period when the temperature of thermocouple i2 is above that corresponding to the electrical potential of the balancing instrument.

The armature of relay 28 is so connected with a timing device, represented in Figure l by cam 29 operated by clockwork 30, that when relay 28 is energized, thus opening contact 3|, the latter will remain open for a predetermined time. As illustrated in Figure 1, this is accomplished by pin 32 which normally engages in slot 33 of cam 29 preventing clockwork 39 from operating. Upon relay 28 becoming energized, pin 32 is withdrawn from slot 33 permitting cam 29 to be rotated by clockwork 39. During rotation of cam 29, pin 32 rides on the surface of cam 29 holding contact 3| open until cam 29 makes one complete revolution and slot 33 is again in position to be engaged by pin 32, which engagement stops the clockwork until relay 28 is again energized. As seen in Figure 1, contact 3| opens the circuit to solenoid 5 from timer 9 through terminals 1 and 8 thereby causing valve 3 to remain closed during the time required for one revolution of cam 29.

Preferably, clockwork 30 is so adjusted that the time for one revolution of cam 29 is greater than that for one revolution of cam 9, so that upon operation of relay 28 (which in turn is due to any rise of temperature of thermocouple l2) valve 3 will skip one scheduled opening, thereby doubling the reflux ratio. If desired, the timing of cam 29 can be adjusted to cause valve 3 to skip two or more scheduled openings upon actuation of relay 28.

In some instances, especially where low reflux ratios are employed, it may be desired to decrease the time of rotation of cam 29, or to eliminate cam 29 entirely. In such cases valve 3 will be closed, contrary to its regular schedule, for only short periods with correspondingly small increase in reflux ratio.

Operation of the apparatus may be readily understood if it is assumed that head I is attached to the distillation column of a laboratory still in which a mixture of two hydrocarbons (for example, a mixture of benzene and toluene) is being distilled. The still may advantageously be equipped with an automatic heater and control giving an approximately constant boil-up rate.

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Also; suitable automatic equipment may besup plied to segregate the distillate product from line 4 into desired cuts. Likewise, if desired, suitable temperature recording apparatus may be added, controlledeither by a separate thermocouple or by the operation of slide I! of potentiometer It; Vaporsrising in head I arecondensed on the surface ofc'oil 2 and the condensate drains into valve 3. At the particular period depicted in Figure l, valve 3 is open and the condensate is drawn off through line 4 to the receiving apparatus.

Timing cam 9 and clockwork it are set for the reflux ratio to be maintained during periods of constant product composition, 1. e. during period's of constant temperature at thermocouple I2. For example, a reflux ratio of 911 may be chosen and cam 9 may be adjusted to close contact H for six seconds every minute. As cam 8 rotates from the position shown contact! I opens breaking the circuit to solenoid 6 and permitting pin 5 to drop into and close valve 3. Condensate from coil 2 will then be diverted to flow back down the column as reflux.

As long as the composition of the vapors in head I remain'constant the temperature of thermocouple [2 will likewise remain constant and the electrical potential developed by the thermocouple at points M and IE will be balanced by the potential between slide H and terminal 23 and no current will flow through galvanometer 20. Clockwork 38, will consequently, remain at slot 33 of cam 29.

Distillation will then proceed at the 9:1 refiux ratio during the recovery of the major part of the lighter constituent of the mixture being distilled, e. g. during the recovery of most of the benzene from a benzene-toluene mixture. As the distillation of the lighter component nears completion some vapors of the heavier component '(e. g. toluene) will reach head I causing a slight rise in the temperature of thermocouple l2 and causing current to flow through galvanometer 29. The needle of galvanometer 20 will accordingly close contact 2| permitting current from battery 2 to flow through relay 2'8 and terminals 27 and 25 f motor It, which latter will rotate worm l8 and move slide I! to a new position on potentiometer l6 and thus re-establish a potential balance with thermocouple l2. When relay 28 is energized, contact 3| will be opened and will remain open for one complete rotation of cam 29 which, for the example chosen, may advantageously be set to rotate in say 65 seconds which period is long enough to cause contact 31' to remain open during one closure of contact i I. Due to the opening of contact '34 no current can flow to solenoid since the circuit is broken between terminals 1 and 3 and valve 3 will remain closed while contact 3! is open. Accordingly, valve 3 will be caused to skip one scheduled opening and will be open for only 6 seconds in two minutes, resulting in a reflux ratio of 1921. This procedure will be repeated as long as the temperature of thermocouple l2 continues to rise, that is until the lighter component has been completely distilled and the operation of the still becomes stabilized on the heavier component.

Although for the purposes of illustration a two component mixture was used in the above example, it is obvious that the operation would be the same with a multi-component mixture. Each product of constant boiling point would be distilled mai'nly at the reflux ratio determined by cam 9 with an approximately double refiuxratid during periods of product change, where high.v

reflux ratios are desired.

It will be obvious from the above description that many variations of the apparatus shown in Figure 1 may be made within the spirit of the invention in its broadest scope; For example; clockwork l0 and/or clockwork may be replaced by a motor of approximately constant speed, or other timing devices may be substituted for cams 9 and 29. Certain thermionic timing devices are known which are adaptable to operate solenoid 6 in a manner similar to that described for timing device 9. Likewise, the opening. of

contact 3! may be caused to stop timing device 9' when contact II is open, instead of directlyv breaking the circuit to solenoid 6 at terminals 1 and 8. As stated above, various forms of balancing pctehtiometers may be used instead of the particular form illustrated. By the use of suit able apparatus, the opening of contact 3! may act directly to close valve 3 or a separate valve suitably located in line 4:.

Figure 2 of the drawings illustrates a preferred variation of the potential balancing and refluxratio changing apparatus embodying thermionic circuits. In Figure 2 there is illustrated in schematic form a thermocouple balancing potentiometer of the general type described in U. S. Letters Patent No. 2,150,006, issued to Parker and Aceves, comprising: thermocouple l2, D. C. to A. C. converter 50, two stages of amplification 5| and 52, and two-phase reversible induction motor 53, which operates worm i8 and-slide H of slide-wire potentiometer I 6. Operation of'the' balancing system may briefly be described as follows:

In converter 55, metal reed 5G is caused to vibrate between the poles of magnet in synchronization with alternating current supplied from source 55 which supplies current to coil '51. The vibrating reed 54 alternately closes contacts 58 and 59 connected to opposite sides ofthes'plit' primary of transformer 65. The center tap of the primary of transformer 60 is connected to slide H. connected to reed 54 and the other terminal of thermocouple I2 is connected to terminal .23

of potentiometer l6. Due to vibration of reed "56,-

any current'in the thermocouple circuitc'aused' by an out-of-b'alanc'e position of slide ll will cause a current to flow alternately in one side and the other of the primary of transformer '66 resulting in an alternating potential inthe secondary of transformer 60 which will be in-phase or 180 out-of-plia's'e with alternating current source 56 dependin upon the direction of flow of current through thermocouple l2. After amplification the resulting potential of the output terminals BI and B2 of stage 52 will,,like- Wise, be in-phase or 180 out-of-phas'e with source 56 depending upon the direction of current flow through thermocouple a higher or lower temperature than corresponds to the position of slide 11. The amplified current from stage 52 is fed to one winding of two-phase motor 53, the other winding being supplied with alternating current from source 64 which is in synchronization with, but out-of-phase with, source 56. Accordingly, motor 53 is caused to rotate in one direction or the other depending upon whether thetemperaeturev of thermocouple i2 is above orb'eloiv tl'iat" corresponding to the setting of slide [1. The re One terminal of thermocouple i2 is" l2, which isdependant upon whether thermocouple 12 is at 7 sulting rotation of motor 53 causes slide I! to move correspondingly along potentiometer l and re-establish balance in the thermocouple circuit.

As is obvious to one familiar with the electronic art, stages 5i, and 52 may be either transformer coupled (as shown, for simplicity of illustration) or they may be resistance coupled. The plate circuits may be fed by battery (as shown) or by alternating current through suitable rectifying means. Likewise, other types of converters may be substituted for converter 50. In one well known potentiometer-recorder on the market, known as the Brown Electronik Continuous- Balance Potentiometer Pyrometer, stage 52 comprises twin diodes whose plate circuits are supplied with alternating current through a split secondary of a transformer whose primary is supplied from source 56. In this instrument the phase of the current from BI and 62 is shifted 90 by use of suitable condensers (not shown) and. the current supplied to motor 53 from source 64 is of the same phase as source 56, all of which is well known in the potentiometer art. Suffice it to say that, for the purposes of the variation of the invention illustrated in Figure 2, one winding of motor 53 is supplied with alternating current which lags or leads the alternating current supplied to the other winding by substantially 90 depending upon the direction of the flow or" current in thermocouple ii.

For the purposes of the invention there is provided transformer 65, which may advantageously have a 1:1 ratio, the primary of which is connected to the output leads 5i and 62 of amplifier stage 52, and the secondary is connected to the control grid of thyratron tetrode 66. A positive cathode bias, indicated by battery 51, is provided of sufficient potential to prevent a plate current in this tube. As an example, cathode bias 6'! may advantageously be from 6 to 15 volts, preferably about 10 volts. The plate of tube 65 is supplied with alternating potential from the secondary of transformer 68, the primary of which is connected to source 5&3. In the plate circuit of tube 66 there are included contact 69 of twopole relay l0 and the coil of relay l2.

Tube 14 is a power tube, which may advantageously be of the pentode or beam power amplifier types, the plate circuit controlling the operation of relay 10. The control grid circuit includes, in series, contact 13 of relay l2 and negative grid bias, represented by battery 3!, of sufficient voltage to prevent tube F4 from conducting when contact 13 is closed. Across the control grid of tube 14 there are placed condenser 2'5 and variable resistance IE3 of sufficient size to maintain a negative charge on the control grid of tube '14 for a desired period of time after contact i3 is opened.

Contact H of relay in is placed in series with the reflux timing circuit illustrated in Figure 1 and takes the place of contact 3! of relay 28 in Figure 1.

The operation of the circuits of tubes 66 and 14 is as follows:

When the potential developed by thermocouple I2 is balanced by potentiometer [6 no alternating current is developed in the output terminals 6i and 62 of stage 52 and no potential is developed by the secondary of transformer During such times tube 66 is cut oii due to positive cathode bias 5?. Contact 13 of relay 12 will then be open due to no current flowing in the plate circuit of tube 66. With contact 73 open,

8 the control grid of tube 14 is at zero potential rel-- ative to its cathode permitting tube 14 to conduct and current will pass through the coil of relay Til closing contacts 69 and II.

When the temperature of thermocouple I2 is below the corresponding position of slide H, i. e. during periods when the temperature of thermocouple l2 may be falling, an alternating potential is produced at terminals 6| and 62 producing an alternating potential at the terminals of the secondary of transformer 65. However, the potential so produced on the grid of tube 65 will be 180 out of phase with the potential produced on the plate of tube 66 by the secondary of transformer 68. Consequently, tube 66 will still be unable to conduct since its plate will be negative when its grid is positive and when the plate is positive the grid will be negative.

However, during periods when the temperature of thermocouple I2 is rising, the potential produced by the secondary of transformer will be in-phase with that produced by the secondary of transformer 68 and tube 66 will conduct permitting current to pass through relay 12, thereby closing contact 13. Upon closure of contact 73 a negative grid bias is established on tube 14 cutting ofi this tube and simultaneously charging condenser 15. When tube 14 is so cut off, current ceases to flow in relay 10 opening contacts 69 and H. Opening of contact 69 cuts ofi the flow of current in tube and opens contact 13 of relay 12. However, due to the charge accumulated on condenser 15, tube 14 will remain cut-off until this charge leaks off through variable resistance 16, after which tube 14 again conducts and relay 'H] closes contacts 69 and H returning the system to normal operation.

Since contact H is in series with the timing circuit of solenoid 5 (Figure 1) the latter will remain inoperative and valve 3 will remain closed as long as contact H is open. By proper choice of the characteristic of condenser I5 and proper setting of resistance '15, the length of time that contact H is open can be regulated to cause valve 3 to miss one or more scheduled openings, thereby increasing the refiux ratio by double or more.

In commercial instruments of the type depicted by converter 50, amplifiers 5! and 52, and motor 53, the output of amplifier :52 may also, even at conditions of balance, contain a component of twice the frequency of source 56. Likewise, the phase of the output of stage 52 may purposely lag the phase of source 56 to permit proper operation of motor 53. In such cases thesecondary of transformer '55 may be tuned to pass only the frequency of source 56 and the phase may be corrected by the addition of condenser 18 and/or resistance 1'! across the secondary of transformer 65.

Also, in commercial instruments stray or transient electrical impulses may be generated of sufiicient magnitude to trigger tube 65. This may be compensated by the addition of resistance 19 in the grid circuit of tube 14 to slow -down the rate of charge of condenser I5 sufiicient that tube 14 will not be cut off by a momentary closing of contact 13. The addition of condenser across relay it] also helps to compensate for stray impulses by permitting relay H! to remain energized for a short period after tube '14 is cut off. The proper values for resistances TI and i9, and for condensers l8 and 80 can readily be determined by one skilled in the electronic art with the aid of the above description.

Summarizing the above descriptions of Figures 1 and 2, the invention, in its broadest aspects may comprise either mechanical, electromechanical, or thermionic means for (a) balancing a thermocouple established in a distilling column, and (b) setting in motion a timing device arranged to increase the reflux ratio of the column for a predetermined period upon any rise of temperature in the column. Various modifications will suggest themselves to the technician Within the scope and spirit of the invention as set forth in the appended claims.

We claim:

1. A temperature responsive apparatus for the control of reflux in a distillation column comprising, an electrically controlled valve for controlling the return or discharge of reflux, an electric circuit for controlling the valve, a timer in the circuit to supply current to the valve according to a selected schedule, a thermocouple in the column, means to balance the electrical potential of said thermocouple, means responsive to an unbalanced condition between the potentials of the thermocouple and said means for balancing to restore the balance of said means for balancing; a second timer, means responsive to an unbalanced potential in one direction to open said circuit and also to start said second timer, said second timer maintaining said circuit open for a fixed period irrespective of the schedule of the first timer.

2. A temperature responsive apparatus for the control of reflux in a distillation column comprising, an electrically controlled valve for controlling the return or discharge of reflux, an electric circuit for controlling the valve, a timer in the circuit to supply current to the valve according to a selected schedule, a thermocouple in the column, means to balance the electrical potential of said thermocouple, means responsive to an unbalanced condition between the potentials of the thermocouple and said means for balancing to restore the balance of said means for balancing; a second timer, means responsive to an unbalanced potential in one direction to establish the reflux-return condition of said circuit and also to start said second timer, said second timer maintaining said reflux-return condition of said circuit for a fixed period irrespective of the schedule of the first timer.

10 3. A temperature responsive apparatus for the control of reflux in a distillation column comprising, a pair of electric terminals adapted to be connected to an electrically controlled valve for controlling the return or discharge of reflux, an electric circuit including said terminals for controlling such valve, a timer in the circuit to supply current to said terminals according to a selected schedule, a second pair of terminals adapted to be connected to a thermocouple in the column, means to balance the electrical potential between said second pair of terminals, means responsive to an unbalanced condition between the potentials of said second pair of terminals and said means for balancing to restore the balance of said means for balancing; a second timer, means responsive to an unbalanced potential in one direction to open said circuit and also to start said second timer, said second timer maintaining said circuit open for a fixed period irrespective of the schedule of the first timer.

LIONEL S. GALSTAUN.

EDWARD R. KEEVER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,967,258 Podbielniak July 24, 1934 1,968,385 Gille July 31, 1934 2,022,809 Kramer Dec. 3, 1935 2,093,644 Podbielniak Sept. 21, 1937 2,203,689 McDonald June 11, 1940 2,275,648 Podbielm'ak Mar. 10, 1942 2,300,742 Harrison et a1 Nov. 3, 1942 2,304,865 Thumim Dec. 15, 1942 2,342,206 McMillan Feb. 22, 1944 2,374,549 McMillan Apr. 24, 1945 2,453,486 Ball Nov. 9, 1948 2,467,008 Brown Apr. 12, 1949 OTHER REFERENCES Stefiens et al., Ind. and Eng. Chem. Anal. E.d.,

vol. 16 (1944), pages 525 to 527.

Ind. and Eng. Chem. Anal. Ed., vol. 17 (1945), pages 47 to 52. 

